A cryosolution infrared and ab initio study of the van der Waals complexes of cyclopentene with hydrogen chloride and boron trifluoride

Abstract

The formation of weak molecular complexes of cyclopentene with HCl and BF 3, dissolved in liquid argon is investigated using infrared spectroscopy. Evidence is found for the formation of 1:1 complexes in which the Lewis acid under study binds to the C C double bond. At higher concentrations of HCl, weak absorption bands due to 1:2 species are also observed. From spectra recorded at different temperatures between 92 and 127 K, the complexation enthalpies for CP·HCl and CP·BF 3 are determined to be −9.5(3) and −16.1(9) kJ mol −1, while for CP·(HCl) 2 a value of −17.0(6) kJ mol −1 is obtained. For the 1:1 and 1:2 complexes, structural and spectral information is obtained from ab initio calculations at the MP2/6-31+G(d) level. Using free energy perturbation Monte Carlo simulations to calculate the solvation enthalpies and statistical thermodynamics to account for zero-point vibrational and thermal contributions, the complexation energies for CP·HCl and CP·(HCl) 2 are estimated from the experimental complexation enthalpies to be −17.4(14) and −34.0(20) kJ mol −1, while the value for CP.BF 3 was derived to be −23.4(22) kJ mol −1. The experimental complexation energies are compared with the theoretical values derived from the MP2/6-31+G(d) potential energy surfaces and with single point energies calculated at the MP2/6-311++G(3df,2pd) level.